WO2025157601A1 - Procédé de production d'un composite - Google Patents

Procédé de production d'un composite

Info

Publication number
WO2025157601A1
WO2025157601A1 PCT/EP2025/050641 EP2025050641W WO2025157601A1 WO 2025157601 A1 WO2025157601 A1 WO 2025157601A1 EP 2025050641 W EP2025050641 W EP 2025050641W WO 2025157601 A1 WO2025157601 A1 WO 2025157601A1
Authority
WO
WIPO (PCT)
Prior art keywords
carrier layer
composite
interval
process according
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/050641
Other languages
English (en)
Inventor
Michael Klostermann
Kai-Oliver Feldmann
Tori ENGELS
Paulina SOWA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Operations GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of WO2025157601A1 publication Critical patent/WO2025157601A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/142—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of polyurethanes with other resins in the same layer
    • D06N3/143—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of polyurethanes with other resins in the same layer with polyurethanes and other polycondensation or polyaddition products, e.g. aminoplast
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers

Definitions

  • the present invention lies in the field of production of composites, especially of textile coatings and imitation leathers, and in the production of the aforementioned materials. It relates to a process for producing a composite, for example a carrier layer coated with a foam layer, to the use of said composite for production of an imitation leather article, to an imitation leather article obtained thereby, and to the use of such an imitation leather article for production of further articles.
  • Imitation leather generally consists of a textile carrier to which a porous polymer layer has been applied, and the latter has in turn been coated with a top layer or a topcoat.
  • the porous polymer layer in this context preferably has pores in the micrometre range and is air- permeable and hence breathable, i.e. permeable to water vapour, but water-resistant.
  • the porous polymer layer often comprises porous polyurethane (PU).
  • PU porous polyurethane
  • PUDs porous polyurethane
  • the solids content is usually in the range of 30-60% by weight.
  • PUDs are mechanically foamed, the foam thus obtained is coated onto a carrier layer (layer thicknesses typically between 300-2000 pm), and then the composite thus produced is cured.
  • the foam layer can be cured either by thermal drying or by wet coagulation.
  • thermal drying the water present in the PUD system evaporates, which results in formation of a film of the polyurethane particles.
  • wet coagulation which is primarily employed in the case of anionically stabilized polyurethane dispersions
  • the coated carrier layer is first treated with a coagulation bath. This generally comprises aqueous solutions of salts or acids through which the coated carrier layer is pulled.
  • the high electrolyte concentration in the coagulation bath greatly attenuates the electrostatic stabilization of the polyurethane dispersion, so as to result in filming of the polyurethane particles and hence to curing of the foam layer here too.
  • the coated carrier layer is often washed with water and finally dried, likewise at relatively high temperatures.
  • the wet coagulation method still has a number of technical shortcomings. For instance, in many cases, there is only inadequate wetting of the foam layer by the coagulation bath during the coagulation, which results in occurrence of unwanted surface defects during the coagulation, for example colour runs or corrugated surface patterns. Furthermore, inadequate wetting leads to only slow curing of the foam layer, which leads to long coagulation times and hence also one process times in the production.
  • the object of the present invention was therefore to overcome the disadvantages of the wet coagulation method that were outlined at the outset.
  • One object was therefore to provide a process by which carrier layers coated with a foam layer can be produced rapidly and in a defect-free manner by wet coagulation.
  • step (viii) drying the coated carrier layer; so as to obtain the composite, characterized in that the coagulation bath in step (v) comprises at least one polyethersiloxane.
  • the process according to the invention permits the production of the composite without surface defects. For instance, during the wet coagulation, it is possible to avoid defects such as unwanted colour runs or corrugated surface patterns.
  • the process according to the invention permits much faster production of a composite comprising at least one carrier layer and at least one foam layer.
  • the foam layer cures much more quickly during wet coagulation, which can reduce process times, which offers process-related benefits both from an environmental and economic point of view.
  • aliphatic encompasses for the purposes of the present invention cyclic and acyclic (non- cyclic), saturated and unsaturated carbon compounds, with express exclusion of aromatic compounds from this term (cf. Compendium of Technical Terminology, Gold Book, International Union of Pure and Applied Chemistry, 2014, version 2.3.3, p. 57).
  • alkyl for the purposes of the present invention encompasses branched and unbranched alkyl groups including cyclic and/or acyclic structural elements, where cyclic structural elements by definition comprise at least three carbon atoms.
  • C1 -C8 alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, hexyl, heptyl and octyl.
  • radicals are selected independently of one another unless stated otherwise. If envisaged in the lists, they may thus be the same or different.
  • the stated indices may represent either absolute numbers or average values. In the case of polymeric compounds, the indices preferably represent average values. Structural and empirical formulae presented in the present invention are representative of all isomers that are conceivable via different arrangement of the repeating units.
  • the processes described hereinafter comprise the process steps mentioned and optionally the optional process steps that are identified as such or other optional steps that are not detailed herein, which can be performed before, between or after the process steps mentioned.
  • the processes described hereinafter comprise the process steps mentioned preferably in the sequence mentioned.
  • step (viii) drying the coated carrier layer; so as to obtain the composite is characterized in that the coagulation bath in step (v) comprises at least one polyethersiloxane.
  • the at least one polyethersiloxane is preferably selected from the group consisting of pendent polyethersiloxanes and linear terminally modified polyethersiloxanes.
  • corresponding polyethersiloxanes can be prepared by reaction of at least one siloxane bearing Si-H groups with at least one polyether having at least one double bond reactive toward Si-H groups, preferably in the form of an allyl group.
  • the chemical reactions forming the basis of this preparation are known in the technical literature and are described extensively therein (see, for example, Silicones - Chemistry and Technology, Vulkan-Verlag Essen, 1989).
  • the reaction of the siloxane bearing Si-H groups with at least one polyether preferably takes place in the presence of at least one catalyst, with particular preference here for platinum catalysts, especially platinum(O) catalysts.
  • platinum catalysts especially platinum(O) catalysts.
  • Such catalysts are known to the person skilled in the art; see, for example, Lewis et al., “Platinum Catalysts used in Silicones Industry”, Platinum Metal Review, 1997, 44(23), 66-74.
  • the polyethers used for production of the polyethersiloxanes according to the invention are preferably polyoxyalkylenes, preferably based on ethylene oxide and propylene oxide. If the polyethers here have more than one alkylene oxide species, the polyethers may be in random distribution (random polymer), in ordered form (block polymer) or in the form of a gradient distribution.
  • the polyethers used for production of the polyethersiloxanes according to the invention may be either OH-functional or terminated. What is meant by “terminated” in this connection is that the polyethers have a -O-R' radical or a carboxyl radical of the -O-C(O)-R" form, where R' and R" represent a monovalent aliphatic, saturated or unsaturated hydrocarbon radical having 1 to 20, preferably having 1 to 10, carbon atoms, most preferably a methyl radical.
  • Pendent polyethersiloxanes in the context of the present invention are especially preferably those that conform to the general formula 1 : where x represents an integer in the interval of 1 to 50, preferably in the interval of 2 to 25, more preferably in the interval of 2 to 15; y represents an integer in the interval of 0 to 250, preferably in the interval of 5 to 150, more preferably in the interval of 5 to 100; each R 1 independently represents a monovalent aliphatic or monovalent aromatic hydrocarbon radical having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, most preferably a methyl radical, each R 2 independently represents an OH-functional or terminated polyether radical, and each R 3 independently corresponds to R 1 or R 2 .
  • Linear terminally modified polyethersiloxanes in the context of the present invention are especially preferably those that conform to the general formula 2: where z represents an integer in the interval of 1 to 100, preferably in the interval of 2 to 50, more preferably in the interval of 3 to 30; each R 4 independently represents a monovalent aliphatic or monovalent aromatic hydrocarbon radical having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, most preferably a methyl radical, and each R 5 independently represents an OH-functional or terminated polyether radical.
  • the carrier layer provided in process step (i) is preferably a flexible carrier layer, more preferably a textile carrier layer.
  • textile carrier layers these are preferably woven, nonwoven or knitted materials based on natural or synthetic fibres and mixtures thereof, for example cotton, polyester, polyester-cotton mixtures, wool, silk, flax, jute, bamboo, nylon, viscose, spandex, aramid or acrylic fibres.
  • the carrier layer may additionally have been pretreated, for example with dyes, pigments, UV absorbers, plasticizers, antioxidants, polymer dispersions or flame retardants.
  • the aqueous polymer dispersion used in process step (ii) is preferably selected from the group of aqueous polystyrene dispersions, aqueous polybutadiene dispersions, aqueous poly(meth)acrylate dispersions, aqueous polyvinylester dispersions and aqueous polyurethane dispersions.
  • the solids content of these dispersions is preferably in the range of 20-70% by weight, more preferably in the range of 35-65% by weight, based on the total weight of the dispersion.
  • aqueous polyurethane dispersions based in particular on polyester polyols, polyesteramide polyols, polycarbonate polyols, polyacetal polyols and polyether polyols.
  • the polymer dispersions are preferably aqueous, meaning that the dispersion medium used is essentially water (i.e. at least 90% by weight, preferably at least 95% by weight).
  • the polymer dispersion used in process step (ii) is anionically stabilized, meaning that the polymer particles in the dispersion have anionically charged groups.
  • Most preferred in this connection are neutralized and partly neutralized acid groups, in particular neutralized and partly neutralized carboxylic acid and sulfonic acid groups.
  • process step (ii) it is possible in process step (ii) to use any foaming aids capable of stabilizing a foam based on at least one polymer dispersion.
  • the function of the at least one foaming aid here is to enable efficient foaming of the mixture provided in process step (iii).
  • the at least one foaming aid should stabilize the foam produced in process step (iii) as well as possible during the further process steps, so as to minimize ageing effects, such as foam drainage or cell coarsening.
  • the at least one foaming aid is used in process step (ii) in a concentration of 0.2-15% by weight, more preferably in the range of 0.4-10% by weight, especially preferably in the range of 0.5-7.5% by weight, based on the total weight of the mixture provided in process step (ii).
  • the at least one foaming aid used in process step (ii) is selected from the group of the polyglycerol esters, especially those obtainable by the esterification of at least one polyglycerol with at least one carboxylic acid.
  • the polyglycerol esters used in process step (ii) are selected from the group consisting of polyglycerol palmitate and polyglycerol stearate.
  • the polyglycerol esters usable as foaming aids in the context the present invention reference is made in full, but without restriction, to EP 3487945 B1 (paragraphs 18-34). More preferably, the polyglycerol ester used in process step (ii) is one conforming to the general formula 3:
  • the mixtures provided in process step (ii) may optionally also contain further additions, for example fillers, organic and inorganic pigments, flatting agents, stabilizers, such as hydrolysis stabilizers or UV stabilizers, antioxidants, absorbers, crosslinkers, levelling additives, thickeners or surfactants.
  • additives for example fillers, organic and inorganic pigments, flatting agents, stabilizers, such as hydrolysis stabilizers or UV stabilizers, antioxidants, absorbers, crosslinkers, levelling additives, thickeners or surfactants.
  • Preferred fillers used in process step (ii) are selected from the group of the silicates, for example talc, mica or kaolin, of the carbonates, for example calcium carbonate or chalk, of the oxides/hydroxides, for example ground quartz, silica, aluminium/magnesium hydroxide, magnesium oxide or zinc oxide, and of the organic fillers, for example chemical pulp, cellulose and cellulose derivatives, lignin, wood fibres/wood flour, ground plastics or textile fibres. It is further preferable when fillers are used in process step (ii) in a concentration of 5-50% by weight, more preferably of 10-45% by weight, even more preferably of 15-40% by weight, based on the total weight of the mixture provided in process step (ii).
  • Preferred thickeners used in process step (ii) are selected from the class of the associative thickeners.
  • Associative thickeners here are substances which lead to a thickening effect through association at the surfaces of the particles present in the polymer dispersions. The term is known to those skilled in the art.
  • Preferred associative thickeners are selected here from polyurethane thickeners, polyacrylate thickeners, polyether thickeners and hydrophobically modified cellulose ethers. Very particular preference is given to polyurethane thickeners.
  • the concentration of the thickeners based on the total weight of the mixture provided in process step (ii) is in the range of 0.01 -10% by weight, more preferably in the range of 0.05-5% by weight, most preferably in the range of 0.1-3% by weight.
  • the mixture is foamed, so as to obtain a foamed mixture.
  • the foaming can be effected here with the aid of shear units familiar to the person skilled in the art, for example Dispermats, dissolvers, Hansa mixers, Oakes mixers or mixers made by Gemata.
  • the mixture is foamed in process step (iii) to a density in the range of 200-850 g/l, more preferably in the range of 300-800 g/l, even more preferably in the range of 400-750 g/l.
  • the carrier layer is coated with the foamed mixture, so as to form a coated carrier layer.
  • Coatings of the foamed mixture can be produced by methods familiar to the person skilled in the art, for example knife coating. It is preferable in the context of the present invention when the foamed mixture is coated on to the carrier layer in process step (iv) in a layer thickness of 100-2000 pm, preferably in the range of 150-1500 pm, even more preferably in the range of 200-1000 pm.
  • the foamed mixture is coated on to the carrier layer in process step (iv) so as to obtain a coat weight in the range of 20-1000 g/m 2 , more preferably in the range of 75-750 g/m 2 , even more preferably in the range of 100-500 g/m 2 .
  • the coated carrier layer is treated with a coagulation bath, which results in coagulation and curing of the carrier layer coated with the foamed mixture.
  • the coagulation bath here contains at least one coagulation agent which is preferably selected from the group consisting of acids and salts.
  • Salts that are particularly preferred in the context of the present invention are selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, calcium chloride and calcium nitrite.
  • Acids that are particularly preferred in the context of the present invention are selected from the group consisting of mineral acids, for example hydrochloric acid, and organic acids, where organic acids are especially preferred. Most preferably, the organic acid is citric acid or lactic acid, and mixtures of these substances.
  • the coagulation agent is present in the coagulation bath in a concentration in the range of 0.5-25% by weight, more preferably in the range of 1- 20% by weight, even more preferably in the range of 2-15% by weight, based on the total amount of the coagulation bath.
  • the coated carrier layer is treated with the coagulation bath in process step (v) for a period of 0.2-15 minutes, preferably of 0.5-12 minutes, more preferably of 1 -10 minutes.
  • the process according to the invention is characterized in that the coagulation bath used in process step (v) comprises at least one polyethersiloxane. It is preferable here when the polyethersiloxane is present in the coagulation bath in a concentration of 0.05-5% by weight, more preferably in the range of 0.1-3% by weight, even more preferably in the range of 0.2-2.5% by weight, based on the total amount of the coagulation bath.
  • excess coagulation liquid can be removed from the coated carrier layer in an optional process step (vi). This is preferably done mechanically, for example by squeezing the coated carrier layer with a drum or a padder. Corresponding techniques are known to those skilled in the art.
  • the coated carrier layer may be washed with water in an additional optional process step (vii), in order to remove further residues of excess coagulation liquid from the coated carrier layer. It is optionally possible to remove residues of the wash water from the coated carrier layer after this washing operation. This is preferably also done mechanically, for example by squeezing the washed coated carrier layer with a drum or a padder.
  • the coated carrier layer is dried, so as to obtain the composite comprising at least one carrier layer and at least one foam layer.
  • this drying is effected at temperatures in the range of 60-170°C, preferably in the range of 70-160°C, more preferably in the range of 80-150°C.
  • Corresponding drying techniques are widespread in industry and are known to those skilled in the art.
  • the invention further provides a composite comprising at least one carrier layer and at least one foam layer, obtained by the process according to the invention.
  • the at least one foam layer of the composite here has an average cell size of up to 250 pm, preferably of up to 150 pm, especially preferably of up to 100 pm, most preferably of less than 75 pm.
  • Average cell size can preferably be determined by microscopy, preferably by electron microscopy.
  • a cross section of the porous polymer coating is viewed by means of a microscope with sufficient magnification and the size of at least 25 cells is ascertained.
  • the magnification of the microscope chosen should preferably be such that at least 10 x 10 cells are present in the observation field.
  • the average cell size is then calculated as the arithmetic average of the cells or cell sizes viewed. This determination of cell size by means of microscopy is familiar to those skilled in the art.
  • the foam layer of the composite of the invention has a layer thickness in the range of 100-2000 pm, preferably in the range of 150-1500 pm, even more preferably in the range of 200-1000 pm. It should be made clear that process steps (v)-(viii) may result in a decrease in the thickness of the foam layer coated on to the carrier layer in process step (iv), for example via loss of water or via mechanical compression.
  • the layer thickness of the foam layer of the composite of the invention therefore need not necessarily be identical to the layer thickness of the foam layer coated in process step (iv).
  • an imitation leather article is considered to mean an article comprising or consisting of imitation leather.
  • Such an imitation leather article can preferably be produced by a process comprising the following process steps:
  • M2 providing at least one aqueous polymer dispersion
  • M3 coating the at least one composite according to the invention with the at least one aqueous polymer dispersion
  • M6 optionally embossing the coated composite; so as to obtain the imitation leather article.
  • the polymer dispersion used in process step M2) is preferably selected from the group of aqueous polystyrene dispersions, aqueous polybutadiene dispersions, aqueous poly(meth)acrylate dispersions, aqueous polyvinylester dispersions and aqueous polyurethane dispersions.
  • the solids content of these dispersions is preferably in the range of 20-70% by weight, more preferably in the range of 35-65% by weight.
  • Particular preference is given in accordance with the invention to aqueous polyurethane dispersions, especially those based on polyester polyols, polyesteramide polyols, polycarbonate polyols, polyacetal polyols and polyether polyols.
  • polymer dispersions used in process step M2) may optionally also contain further additions, for example fillers, organic and inorganic pigments, flatting agents, stabilizers, such as hydrolysis stabilizers or UV stabilizers, antioxidants, absorbers, crosslinkers, levelling additives, thickeners or surfactants.
  • stabilizers such as hydrolysis stabilizers or UV stabilizers, antioxidants, absorbers, crosslinkers, levelling additives, thickeners or surfactants.
  • the polymer dispersion is coated onto the composite according to the invention, so as to form a coated composite.
  • Coatings of the polymer dispersion can be produced by methods familiar to the person skilled in the art, for example knife coating. It is preferable in the context of the present invention when the polymer dispersion is coated onto the composite in process step M3) in a layer thickness of 25-500 pm, preferably in the range of 50-300 pm, even more preferably in the range of 75- 250 pm.
  • the coated composite is dried.
  • this drying is effected at temperatures in the range of 60-170°C, preferably in the range of 70-160°C, more preferably in the range of 80-150°C.
  • Corresponding drying techniques are widespread in industry and are known to those skilled in the art.
  • the coated composite after being dried, and optionally after application of further top layers in an optional process step M5), may be embossed in a process step M6).
  • embossment it is possible to apply a surface structure to the coated composite, for example in the form of a typical leather grain.
  • the coated composite is preferably embossed in process step M6) at elevated temperatures and pressures, for example by the use of heated plates or rolls that have a negative impression of the desired surface structure.
  • Corresponding embossing techniques are known to those skilled in the art.
  • the imitation leather article contain at least one composite according to the invention can be produced by an alternative process comprising the following process steps:
  • the release paper provided in process step N1) is selected such that an aqueous polymer dispersion can be coated onto it in a defect-free manner and has good detachability in the dried state.
  • Especially preferred here are wax- or silicone-coated release papers.
  • Corresponding release papers are known to those skilled in the art.
  • the aqueous polymer dispersion used in process step N2) is preferably selected from the group of aqueous polystyrene dispersions, aqueous polybutadiene dispersions, aqueous poly(meth)acrylate dispersions, aqueous polyvinylester dispersions and aqueous polyurethane dispersions.
  • the solids content of these dispersions is preferably in the range of 20-70% by weight, more preferably in the range of 35-65% by weight.
  • Particular preference is given in accordance with the invention to aqueous polyurethane dispersions, especially those based on polyester polyols, polyesteramide polyols, polycarbonate polyols, polyacetal polyols and polyether polyols.
  • polymer dispersions used in process step N2) may optionally also contain further additions, for example fillers, organic and inorganic pigments, flatting agents, stabilizers, such as hydrolysis stabilizers or UV stabilizers, antioxidants, absorbers, crosslinkers, levelling additives, thickeners or surfactants.
  • stabilizers such as hydrolysis stabilizers or UV stabilizers, antioxidants, absorbers, crosslinkers, levelling additives, thickeners or surfactants.
  • the polymer dispersion is coated onto the release paper, so as to form a coated release paper.
  • Coatings of the polymer dispersion can be produced by methods familiar to the person skilled in the art, for example knife coating. It is preferable within the context of the present invention when the polymer dispersion in process step N4) is applied to the composite in a layer thickness of 25- 500 pm, preferably in the range of 50-300 pm, even more preferably in the range of 75-250 pm.
  • the coated release paper is dried.
  • this drying is effected at temperatures in the range of 60-170°C, preferably in the range of 70- 160°C, more preferably in the range of 80-150°C.
  • Corresponding drying techniques are widespread in industry and are known to those skilled in the art.
  • process step N5 a further layer of polymer dispersion is applied to the already coated release paper, the same constraints as already described for process step N2) are applicable to the polymer dispersion. Either identical or different polymer dispersions may be used for process steps N2) and N5). The same constraints as already described for process step N4) are likewise applicable to the coating of the polymer dispersion in process step N5).
  • process step N7) the composite laminated onto the coated release paper is dried to obtain the imitation leather article.
  • the same constraints as for process step N5) are applicable to the temperature provisions in this step.
  • the imitation leather article obtained in this process step is finally detached from the release paper in a process step N8).
  • the present invention further provides for the use of at least one imitation leather article according to the invention for production of an article, where the article is preferably selected from the group consisting of shoes, insoles, bags, suitcases, small cases, textiles, clothing, automobile parts, especially seat covers, coverings of door parts, dashboard parts, steering wheels and/or handles, and gearshift gaiters, fitout articles such as desk pads, cushions and seating furniture, and cushioning and damping materials in medical applications.
  • the article is preferably selected from the group consisting of shoes, insoles, bags, suitcases, small cases, textiles, clothing, automobile parts, especially seat covers, coverings of door parts, dashboard parts, steering wheels and/or handles, and gearshift gaiters, fitout articles such as desk pads, cushions and seating furniture, and cushioning and damping materials in medical applications.
  • HYDROTECH® MT 480 is an aliphatic polyether-based polymer dispersion from ERCA;
  • ORTEGOL® P 2 is a foaming aid for aqueous polymer dispersions from EVONIK;
  • ORTEGOL® PD 152 is a dispersing additive from Evonik.
  • ORTEGOL® PV 301 polyurethane-based associative thickener from Evonik Industries AG; kaolin was sourced from SIGMA ALDRICH as mineral filler; ECO PIGMENT® BLACK is a water-based black colour paste from Cromogenia
  • Lactic acid in technical grade quality was sourced from Sigma-Aldrich
  • the efficacy of the process according to the invention was tested by conducting a number of coagulation experiments with foam-coated textiles.
  • the textile carrier layer used for these experiments was a woven polyester-cotton blend textile, onto which a foamed polyurethane dispersion had been coated.
  • the mixtures described in Table 1 were provided and foamed mechanically.
  • the mixture thus foamed was coated onto the abovementioned textile carrier layer. This was done with the aid of the Labcoater LTE-S coating apparatus from Mathis AG. The layer thickness of the foam layer was 800 pm. Directly thereafter, the coated textile carrier layers were treated with different coagulation baths. The composition of the coagulation baths is compiled in Table 2. Table 2: Summary of the composition of the coagulation baths used
  • the coated textile carrier layers were weighted down and immersed into the respective bath.
  • a laboratory spatula was used to determine the extent to which the foam coating had cured in a time interval of 30 seconds. It was possible here to observe that the curing times were distinctly different depending on the bath.
  • Coated carrier layers which had been treated with bath #1 cured after about 9 minutes, whereas samples which had been treated with bath #2 and bath #3 had already cured completely after 6 and 4 minutes respectively.
  • the cured samples were then treated with a laboratory padder in order to remove excess coagulation liquid and then washed 4 times with water. After each washing operation, the samples were treated again with a laboratory padder in order to remove excess wash water.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

La présente invention se rapporte au domaine de la fabrication de composites, notamment de revêtements textiles et de similicuirs, et à la fabrication des matières précitées. L'invention concerne un procédé de production d'un composite, par exemple une couche de support revêtue d'une couche de mousse, l'utilisation dudit composite pour la production d'un article en similicuir, un article en similicuir obtenu au moyen de celui-ci, et l'utilisation d'un tel article en similicuir d'imitation pour la production d'autres articles.
PCT/EP2025/050641 2024-01-22 2025-01-13 Procédé de production d'un composite Pending WO2025157601A1 (fr)

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EP24153193 2024-01-22
EP24153193.8 2024-01-22

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US20180016406A1 (en) * 2015-03-03 2018-01-18 Evonik Degussa Gmbh Production of porous polyurethane layers
CN108411640A (zh) * 2018-04-03 2018-08-17 浙江丰望环保有限公司 一种皮革及其制备方法
CN110452359A (zh) * 2019-08-15 2019-11-15 台州禾欣高分子新材料有限公司 一种pu镜面革用聚氨酯湿法树脂的制备与应用
EP3487945B1 (fr) 2016-07-19 2020-05-13 Evonik Operations GmbH Utilisation d'esters de polyols destines a la production de revetements plastiques poreux
CN114687221A (zh) * 2022-03-29 2022-07-01 苏州瑞高新材料有限公司 一种耐磨发泡pu层、合成革及其制备方法
CN115287914A (zh) * 2022-09-13 2022-11-04 山东同大海岛新材料股份有限公司 生物基超纤革及其加工方法

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EP3487945B1 (fr) 2016-07-19 2020-05-13 Evonik Operations GmbH Utilisation d'esters de polyols destines a la production de revetements plastiques poreux
CN108411640A (zh) * 2018-04-03 2018-08-17 浙江丰望环保有限公司 一种皮革及其制备方法
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